Process for the preparation of aminoazo dyes

ABSTRACT

Preparation of water-soluble reactive dyes containing vinylsulphonyl and β-sulphatoethylsulphonyl groups by the oxidation of dyes containing β-hydroxyethylmercapto radicals, and then sulphation and, if appropriate, conversion of the β-sulphatoethylsulphonyl radical to the vinylsulphonyl radical with bases.

This is a division of application Ser. No. 08/041,741 (filed on Apr. 1,1993) now U.S. Pat. No. 5,432,266; which is a continuation-in-part ofapplication Ser. No. 07/898,859 (filed on Jun. 15, 1992), now abandoned.

Various processes for the preparation of reactive dyes are alreadyknown, but they are not always satisfactory.

The invention relates to (A) a process for the preparation ofwater-soluble reactive dyes containing vinylsulphonyl (orβ-sulphatoethylsulphonyl) groups, of structure (1) (B) to novelfibre-reactive monoazo and disazo dyes of the structure (Ia), and (C) toa process for colouring polyurethane plastics with monoazo dyestuffs,some of which are new.

In aspect (A) the reactive dyes are of structure (I)

    [A]--(SO.sub.2 X).sub.1 or 2                               ( 1)

wherein

A=a chromophoric radical from the azo, polyazo, anthraquinone, formazaneor triphendioxazine series, which is preferably substituted by at leastone --SO₃ H group, and

X=CH═CH₂ or CH₂ CH₂ OSO₃ H,

and are produced by oxidizing and sulphating mercapto compounds of thestructure

    [A]--(S--CH.sub.2 --CH.sub.2 --OH).sub.1 or 2

and, if appropriate, the sulphatoethylsulphonyl radical is converted tothe vinylsulphonyl radical with bases.

Although Japanese patent document A-44 24 899 has already disclosed aprocess for the preparation of β-sulphatoethylsulphonyl-substituted dyesby the oxidation of a thioether, said process is restricted tophthalocyanines.

With regard to aspect (B), the present invention further relates tonovel fibre-reactive monoazo and disazo dyes of the structure ##STR1##wherein D=a radical of a diazo component from the benzene or naphthaleneseries, which, in addition to any desired number of sulpho or carboxylgroups, can also contain substituents, preferably C₁ -C₄ -alkyl, C₁ -C₄-alkoxy, phenoxy, halogen, acetylamino, benzoylamino, ureido,phenylsulphonyl or C₁ -C₄ -alkylsulphonyl, and unsubstituted orsubstituted phenylazo or naphthylazo substituents and fibre-reactivegroups such as SO₂ X, CH₂ SO₂ X or heterocyclic pyrimidine- ortriazine-reactive systems, excepted substituents being OH, NH₂,monoalkylamino or dialkylamino, or arylamino--such as anilino,

X=CH═CH₂ or CH₂ CH₂ OSO₃ H and

Y═H, C₁ -C₆ -alkyl, Cl--, OH--, CN-- CO₂ H--, OSO₃ H--, SO₃ H--, SO₂ X--or C₁ -C₄ -alkoxy-substituted C₁ -C₆ -alkyl, allyl, cycloalkyl, such asfor example cyclohexyl, cyclopentyl or cyclopropyl, CO₂ H--, OSO₃ H-- orSO₃ H-substituted cycloalkyl, benzyl or OH--, CO₂ H-- or SO₃H-substituted benzyl, but in particular CH₂ CH₂ OSO₃ H,

R=H, C₁ -C₄ -alkyl, Cl--, OH--, CN--, CO₂ H--, OSO₃ H--, SO₃ H--, SO₂X-- or C₁ -C₄ -alkoxy-substituted C₁ -C₄ -alkyl, allyl, benzyl or OH--,CO₂ H-- or sulpho-substituted benzyl, but in particular H.

The grouping NR--Y also represents a saturated N-heterocycle, such as,for example: ##STR2##

Substituents on the phenylazo and naphthylazo group are preferablysulpho, carboxy, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen, SO₂ X and --CH₂SO₂ X.

German patent document A-3 512 340, a representative compound of whichbeing e.g. Example 32 of the formula ##STR3## wherein the azo group,which links the ureido substituted phenyl and the triazine rest shouldbe a --NH-group has already disclosed azo-reactive dyes whichsimultaneously carry a β-sulphatoethylsulphonyl radical and aβ-sulphatoethylamino radical on a phenyl radical. However, these groupsare part of the diazo component whereas, according to the invention,these groups are part of the coupling component.

Preferred dyes are those of structures (2) and (3): ##STR4## wherein D=aphenylene or naphthylene radical which can additionally be substitutedby carboxyl, C₁ -C₁ -alkyl, C₁ -C₄ -alkoxy, phenoxy, halogen, C₁ -C₄-alkylsulphonyl, SO₂ X, CH₂ SO₂ X or a fibre-reactive heterocyclicpyrimidine- or triazine-reactive radical, it being possible for themeanings of both groups --D-- in formula (3) to be identical ordifferent.

It is particularly preferable to us9 bifunctional fibre-reactive dyes ofstructures (4) to (8): ##STR5## wherein n=0or 1,

R¹ =H or C₁ -C₄ -alkyl,

Z=a fibre-reactive halogen-containing radical from the triazine orpyrimidine series,

D=a phenylene or naphthylene radical which can additionally besubstituted by carboxyl, methyl, ethyl, methoxy, ethoxy, chlorine,bromine or fluorine, it being possible for the meanings of both groups Din formulae (6) , (7) and (8) to be identical or different, and

R, X and Y are as defined under formula (1a).

The fibre-reactive radical Z represents chlorine- or fluorine-containingtriazine or pyrimidine radicals such as e.g. those described in Europeanpatent document A-395 951, preferably a monofluoro- or monochloro-triazine radical or a 5-chloro-2,6-difluoro-4-pyrimidinyl or5-chloro-6-fluoro-4-pyrimidinyl radical. Selected dyes are those ofstructures (9) to (19): ##STR6## wherein R² =H, CH₃, OCH₃, Cl or CH₂ SO₂X

and the other substituents n, R¹, Z, X and Y are as defined underformula (8) .

Of these selected types of dye of structures (9) to (19), it isparticularly preferable to use those in which the radical Y=CH₂ CH₂ OSO₃H, such as e.g. dyes of structures (20) to (31): ##STR7## wherein thesubstituents are as follows: R¹ =H or C₁ -C₄ -alkyl,

R² =H, CH₃ , OCH₃, Cl or CH₂ SO₂ X,

X=--CH═CH₂ or --CH₂ CH₂ OSO₃ H and

Z is as defined under formula (8).

The preparation of the dyes (1a), wherein A from formula (1) is to betreated as equivalent to the radical ##STR8## is carried out byoxidising thio compounds of structure (32): ##STR9## wherein Y=is asdefined under (1a), and is in particular CH₂ CH₂ OH, and

D and R are as defined under (1a),

as described in European patent document A-137 417 to sulphones ofstructure (33): ##STR10## and sulphating the latter in known manner togive (1a) in which X=CH₂ CH₂ OSO₃ H.

In this reaction hydroxyalkyl groups in R and Y in (33) are convertedinto sulphatoalkyl groups.

One particular embodiment of the process consists in oxidising compoundsof the structure

    [A]--(S--C.sub.2 H.sub.4 --OH).sub.1 or 2                  ( 34)

or (32) in an aqueous medium with hydrogen peroxide solution, ifappropriate under catalysis with tungstate or vanadate, at temperaturesin the range from 20° to 100° C., preferably at 60°-80° C., and at pHvalues of between 5 and 10, preferably of between 7 and 9, andsulphating the resulting isolated sulphones in concentrated sulphuricacid, sulphuric acid monohydrate, oleum or sulphur trioxide, attemperatures of between 0° and 40° C., to give (1) or (1a) in whichX=sulphatoethyl.

Dyes in which X=vinyl are produced by known procedures from those inwhich X=sulphatoethyl at elevated pH values, for instance at pH 9-11.

Another preferred embodiment of the process consists in carrying out thesulphation and oxidation simultaneously by reacting compounds (34):

    [A]--(S--C.sub.2 H.sub.4 --OH).sub.1 or 2                  ( 34)

or (32) with peroxodisulphates in concentrated sulphuric acid, sulphuricacid monohydrate or oleum at 10°-50° C.

The intermediates of structure (32) are obtained by the azo coupling ofdiazotised [D]--NH₂ with compounds of structure (35): ##STR11##

These coupling components (35) can be prepared by ethoxylatingo-aminothiophenol and N-substituted o-aminothiophenols with ethyleneoxide or chloroethanol under alkaline conditions. The component (35) inwhich R=H and Y¹ =CH₂ CH₂ OH can be obtained by reacting benzthiazole,ethylene oxide and water and then hydrolysing the resulting N-formylcompounds (36): ##STR12##

R-Substituted o-aminothiophenols are obtained simply by alkylatingbenzthiazole and then hydrolysing the ammonium compounds (37): ##STR13##with ring opening.

Another method of preparing compounds (35) comprises alkylatingprecursors of the formula ##STR14## wherein G=NH₂, NHR or NHY.

The alkylation can be carried out for example with alkyl halides R-Halor Y-Hal, in which Hal=Cl, Br, or F, or with activated olefins, such asfor example acrylic acid derivatives or vinyl sulphonyl derivatives, orby reduction with aldehyde derivatives.

Preferred coupling components (35) are those in which the radicals R andY are substituted by a sulpho, carboxyl or, in particular, a hydroxylgroup.

Reactive dyes of structure (7) can also be prepared by oxidising andthen sulphating thio compounds of structure (38): ##STR15##

Corresponding intermediates (38) are obtained e.g. by diazotising thiocompounds of formula (39): ##STR16## or (32) in which Y and R=H and thencoupling the products with compounds of structure (35).

Reactive dyes of structure (5) can also be prepared by condensing dyesof structure (40): ##STR17## which can be obtained as described for(1a), with a heterocyclic reactive component Z-Hal, wherein Hal=Cl or F,in the presence of acid-binding agents, in known manner. Thispreparative process can also be applied to the dyes (8) .

The formulae given are those of the free acids. The preparationgenerally produces the salts, especially the alkali metal salts such asthe sodium, potassium or lithium salts.

The novel dyes according to the invention are suitable for dyeing andprinting materials containing hydroxyl and amide groups, especially wooland cellulose materials. They are distinguished by a high reactivity anda high degree of fixation. The yellow, orange and brown dyeings andprints obtainable with these dyes are moreover distinguished by a highfibre-dye bond stability and by an outstanding stability towardsoxidising agents such as detergents containing peroxide or chlorine.

The dyes can be used as both solid formulations and concentratedsolutions. They are also suitable for use in mixtures with otherreactive dyes, especially for trichromatic dyeing.

Pursuant to aspect (C) hereinabove, the invention also relates to aprocess for colouring polyurethane plastics using monoazo dyestuffswhich are suitable for incorporation in the plastic with the formationof covalent bonds. Such dyestuffs for polyurethane plastics aredisclosed, for example, in U.S. Pat. No. 4,751,254 and GB-A-1,472,379,but have some disadvantages with respect to the demands made on them. Aprocess for colouring polyurethane plastics with dyestuffs has now beenfound which is characterised in that at least one dyestuff of theformula ##STR18## in which A represents phenylene or naphthylene, eachof which is optionally substituted by alkyl or halogen,

E represents C₁ -C₄ -alkylene,

R¹ represents hydrogen or represents a C₁ -C₆ -alkylene radical which isoptionally substituted by --Cl, --CN, amino, alkylamino, dialkylamino,C₁ -C₄ -alkoxycarbonyl, aminocarbonyl and/or phenyl,

R², R³, R⁴ and R⁵ independently of one another represent hydrogen,halogen, hydroxyl, amino, acylamino or C₁ -C₆ -alkyl, or C₁ -C₆ -alkoxy,mono-or di-C₁ -C₆ -alkylamino, C₁ -C₆ -alkylthio, C₁ -C₆ -alkysulphoxideor C₁ -C₆ -alkylsulphonyl, each of which is optionally substituted byhydroxyl or C₁ -C₄ -alkylene oxide units, or two of these radicalscomplete a fused benzene ring, which is optionally substituted,

m represents a number from 1 to 4, preferably 1 or 2

n represents a number from 0 to 2,

x represents 1 or 2, and

y represents 0 or 1,

the sum of x and y being 2,

is added to the reaction mixture or to one of the starting componentsbefore or during the polyaddition reaction.

A process using dyestuffs of the formula ##STR19## in which A represents1,2-, 1,3- or 1,4 -phenylene or 2,6-naphthylene, each of which isoptionally substituted by methyl, ethyl, chlorine or bromine,

R², R³ and R⁴ independently of one another represent hydrogen, methyl,ethyl, n-propyl, isopropyl, chlorine, acylamino or methoxy,

i denotes the number 0 or 1,

k denotes a number from 1 to 4,

z denotes a number from 0 to 2, and

E, R¹, m, x and y have the abovementioned meanings,

is of particular interest in this context.

In a very particularly preferred process variant, dyestuffs of theformula ##STR20## in which R¹ represents hydrogen, methyl, ethyl, benzylor 2-cyanoethyl and

R², R³ and R⁴ independently of one another represent hydrogen, methyl,ethyl, methoxy, acetylamino or chlorine and

k denotes a number from 1 to 4, preferably from 1 to 2,

m denotes a number from 1 to 4, preferably from 1 to 2,

and i, x, y and z have the abovementioned meanings,

are used for colouring polyurethane plastics.

The invention also relates to novel monoazo dyestuffs of the formula##STR21## in which A represents phenylene or naphthylene, each of whichis optionally substituted by alkyl or halogen,

E represents C₁ -C₄ -alkylene,

R¹ represents hydrogen or represents a C₁ -C₆ -alkylene radical, whichis optionally substituted by --Cl, --CN, amino, alkylamino,dialkylamino, C₁ -C₄ -alkoxycarbonyl, aminocarbonyl and/or phenyl,

R², R³ and R⁴ independently of one another represent hydrogen, halogen,hydroxyl, amino, acylamino or C₁ -C₆ -alkyl, or C₁ -C₆ -alkoxy, mono-ordi-C₁ -C₆ -alkylamino, C₁ -C₆ -alkylthio, C₁ -C₆ -alkylsulphoxide or C₁-C₆ -alkylsulphonyl, each of which is optionally substituted by hydroxylor C₁ -C₄ -alkylene oxide units, or two of these radicals complete afused benzene ring, which is optionally substituted,

m represents a number from 1 to 4,

n represents a number from 0 to 2,

x represents 1 or 2, and

y represents 0 or 1,

z represents 0, 1 or 2,

k represents a number from 1 to 4,

the sum of x and y being 2.

Preferred embodiments are dyestuffs of the formula ##STR22## in which Arepresents 1,2-, 1,3- or 1,4-phenylene or 2,6-naphthylene, each of whichis optionally substituted by methyl, ethyl, chlorine or bromine,

R¹ represents hydrogen or represents a C₁ -C₆ -alkylene radical which isoptionally substituted by --Cl, --CN, amino, alkylamino, dialkylamino,C₁ -C₄ -alkoxycarbonyl, aminocarbonyl and/or phenyl,

R², R³ and R⁴ independently of one another represent hydrogen, methyl,ethyl, n-propyl, isopropyl, chlorine, acylamino or methoxy,

k represents a number from 1 to 4,

z represents a number from 0 to 2,

m represents a number from 1 to 4,

x represents 1 or 2 and

y represents 0 or 1.

A particularly preferred embodiment comprises dyestuffs according to theinvention of the formula ##STR23## in which R¹ represents hydrogen,methyl, ethyl, benzyl or 2-cyanoethyl and

R², R³ and R⁴ independently of one another represent hydrogen, methyl,ethyl, methoxy, acetylamino or chlorine and

k represents a number from 1 to 4, preferably from 1 to 2,

z represents a number from 0 to 2,

m represents a number from 1 to 4, preferably from 1 to 2,

x represents 1 or 2 and

y represents 0 or 1.

The dyestuffs can be prepared, for example, by coupling diazotisedamines of the formula

    HO--C.sub.2 H.sub.4 --O.sub.2 S--(CH.sub.2).sub.n --A--NH.sub.2(V)

in which A and n have the abovementioned meanings, with couplingcomponents of the formula ##STR24## in which E, R¹, R², R³, R⁴, R⁵, m, xand y have the above-mentioned meanings, in accordance with processescustomary per se, as described, for example, in U.S. Pat. No. 4,271,072.

Coupling components of the formula V can also be in the form of mixtureswith randomly distributed alkylene oxide units, such as are obtained,for example, on reaction of primary or secondary aromatic amines withalkylene oxides.

Dyestuffs of the formula III or IV in which i is 1 and z is 1 or 2 anddyestuffs of the formulae VII, VIII and IX in which, z is 1 or 2 can beprepared by oxidation of dyestuffs of the formula III or IV in which iis 1 and z is 0 or, respectively, or dyestuffs of the formulae VII, VIIIand IX in which z is 0, using oxidising agents such as, for example,hydrogen peroxide, peracetic acid and the like, if appropriate in thepresence of oxidation catalysts (for example tungsten(VI) oxide, sodiumtungstate and the like) at temperatures of 0°-100° C. If the oxidationis carried out in water as the solvent, the reaction can be carried outat pH values of 0-10, preferably at pH 2 to 10, if appropriate with theaddition of a buffer system such as, for example, acetic acid/sodiumacetate.

The process according to the invention for colouring polyurethaneplastics is generally carried out by adding the dyestuff of the formula(I) in a suitable form either to the polyol component or thepolyisocyanate component or to the reaction mixture, before or duringpolyurethane formation. The subsequent reaction is carried out in theconventional manner, i.e. in the same way as for uncoloured polyurethaneplastics. Data on this are to be found, for example, in G. Oertel,Kunststoff-Handbuch (Plastics Handbook), volume 7, Polyurethane(Polyurethanes), Hanser, Munich, Vienna 1983; English edition 1985.

The dyestuffs can be added in bulk in the form of dyestuff powder orgranules, but more appropriately in the form of a solution or dispersionin a suitable solvent or dispersing medium, both the individualdyestuffs and dyestuff mixtures being suitable.

The polyurethane plastics coloured by the process according to theinvention can be used for very diverse applications, for example ascompression mouldings, films, fibres, foams, paints and coatingmaterials.

In addition to the characteristic urethane groupings in themacromolecule, the polyurethanes can also contain yet further functionalgroups, such as amide, urea or carbodiimide groups.

Solutions or dispersions in high-boiling organic liquids, for examplealiphatic or aromatic esters of phosphoric acid, phosphonic acid,phthalic acid or adipic acid, such as diphenyl isopropyl phosphate,diphenyl cresyl phosphate, diphenyl octyl phosphate, trichloroethylphosphate and tributyl phosphate or dioctyl phthalate, butyl benzylphthalate and dibutyl phthalate or dioctyl adipate and octyl benzyladipate, lactones, for example butyrolactone, alcohols, in particularliquid polyalcohols, for example octaethylene glycol and condensationproducts of adipic acid and 1,3-butanediol or 1,2-propanediol, ketonesor ethers, having boiling points above 180° C. and vapour pressuresbelow 1 mbar at 20° C., have proved suitable for the preparation offoams. The polyurethane foams coloured in this way can be not onlyflexible, semi-rigid or rigid foams but also polyurethane integralfoams.

The polyurethane thermoplastics coloured by the process according to theinvention, which are used to produce mouldings by injection moulding,extrusion or calendering, are preferably obtained by adding thedyestuff, dissolved or dispersed in a polyol or a diol used as a chainextender, to the reaction mixture or to one of the components,preferably the polyol compound.

Suitable polyols are both hydroxyl group-containing polyesters, inparticular reaction products of dihydric alcohols with dibasiccarboxylic acids, and hydroxyl group-containing polyethers, inparticular addition products of ethylene oxide, propylene oxide, styreneoxide or epichlorohydrin with water, alcohols or amines, preferablydialcohols.

Chain-extending diols are, for example, ethylene glycol, diethyleneglycol, butanediol, hexanediol, octanediol andhydroquinone-β-dihydroxyethyl ether.

If monoalcohols or monoamines are also used to prepare the thermoplasticpolyurethane, the dyestuff can be dissolved or dispersed in thesereagents also. Suitable monoalcohols are, for example, hexanol, octanol,nonyl alcohol or isooctanol.

The polyurethane systems coloured by the process according to theinvention with the dyestuffs of the formula (I) are also suitable fortextile coating. The coloured polyurethanes can be used in the form ofpowders, solutions, granules or dispersions. Chemical and applicationsdetails can be taken from the specialist literature, for exampleMelliand Textilberichte 53, 1272 to 1277 (1972); 52, 1094 to 1099(1971); 51, 1313 to 1317 (1970).

In the case of coating powders, the dyestuff to be used in the processaccording to the invention is most expediently dispersed in the polyolcomponent before a prepolymer is prepared by reaction with adiisocyanate, which prepolymer is reacted in the final stage with adiamine, with chain extension, to give a coloured, free-flowing,thermoplastic polyurethane powder.

In the case of the solutions of the one-component polyurethane coatingcompositions and in the case of the aqueous dispersions, the dyestuff ismost simply added to the polyol component during the preparation of thepolyurethane and incorporated in the polyurethane molecule during thereaction with the diisocyanate. In the case of two-componentpolyurethane textile-coating compositions, the dyestuff can either beincorporated in the crosslinkable polyurethane or can be admixed in theform of a paste, dispersed in a suitable medium, for example a solutionof a polyester-polyurethane in methylethyl glycol/toluene, to thecrosslinkable polyurethane, the incorporation of the dyestuff beingcompleted in the final reaction step during the reaction with adiisocyanate.

Polyurethane elastomers, from which elastomer filaments can be preparedby conventional processes, can be coloured using dyestuffs of theformula (II).

To this end the dyestuff is finely dispersed in the dihydroxy componentbefore a NCO group-containing prepolymer, in which the dyestuff ischemically incorporated, is prepared by reaction with a diisocyanate.

A polyurethane elastomer solution is obtained in solution from theprepolymer by reaction with a diamine serving as chain extender and canbe processed by the dry or wet spinning process to give filaments, or,by spreading the elastomer solution on glass plates and drying, forexample for 30 minutes at 70° C. and 45 minutes at 100° C., to givefilms.

Details on the preparation of polyurethane elastomer solutions can betaken, for example, from German Offenlegungsschrift DE-A-1,962,602.

The process for colouring polyurethane paints using dyestuffs of theformula (I) is expediently carried out by dissolving the dyestuff in thesolution which contains the polyisocyanate component and polyolcomponent. The coloured paint is then applied to the surface to bepainted and stoved, for example for 30 minutes at 180° C., the dyestuffbeing incorporated in a manner which is very fast to overpainting andbleeding.

The dyestuffs are expediently used in a concentration of 0.005 to 1.0%by weight, preferably 0.05 to 0.5% by weight, with respect to the polyolcomponent, in all applications.

Yellow- to red-coloured polyurethane plastics for very diverse fields ofapplication which are distinguished by a very good fastness level areobtained by the process according to the invention.

Compared with the dyestuffs described in GB-A-1,472,379 and U.S. Pat.No. 4,751,254, the dyestuffs according to the invention have adistinctly improved incorporation capacity coupled with outstandingthermal stability and photostability.

The preparation and use will be illustrated by means of the followingexamples, wherein unless otherwise stated, the percentages denotepercentages by weight and parts denote parts by weight.

PREPARATION OF INTERMEDIATES EXAMPLE 1

An emulsion of 135 g of benzothiazole and 1 g of a conventionalemulsifier in 500 ml of water is heated to 60° C. and nitrogen is passedthrough for 1 hour. Over a period of approx. 12 hours, a total ofapprox. 300 g of ethylene oxide are then metered in so as to maintain apH of between 9.5 and 10.5. The reaction is followed by thin layerchromatography. As soon as less than 1% of the initial concentration ofthe benzothiazole is detectable, the introduction of ethylene oxide isstopped and the reaction solution is heated at 80° C. for a further 2hours with the passage of a vigorous stream of nitrogen. After theresidual ethylene oxide has been removed in this way, the approx. 800 mlof reaction solution are cooled to room temperature. In addition toglycol and small amounts of polyglycols, the reaction solution containsthe relatively pure hydroxyethylaniline derivative of the formula##STR25## and can be directly reacted further.

To characterise the product, an 80 ml sample of the solution at pH 7 isworked up by extraction and distillation to give a viscous colourlessoil, to which the above structure can be assigned on the basis of the ¹H NMR and IR data.

IR (NuJol mull): 1662 cm⁻¹ (CO vib.)

¹ H NMR (d₆ -DMSO): δ=3.05 (2H, m); 3.48 (2H, m); 3.60 (2H, m); 3.65(2H, m); 4.68 (t, OH); 4.94 (t, OH); 7.15-7.50 (m, 4H); 8.00 (s, CHO).

Mass spectrum: m/e=241 (M⁺,45%); 213 (M⁺ -CO, 45%); 182 (65% ); 164 (55%); 136 (100% ).

EXAMPLE 2

200 ml of 70% sulphuric acid are added to 800 ml of the reactionsolution of Example 1 and the mixture is heated at 90°-95° C. for onehour. It is then cooled, neutralised with concentrated sodium hydroxidesolution, with external cooling, and then adjusted to pH 12.5, acolourless oil separating out.

(However, the reaction solution of Example 1 can also be hydrolysedunder alkaline conditions by adjusting the pH to 12.5-13.0 with sodiumhydroxide solution and heating at 80°-85° C. for 30 minutes.)

The oil is separated of#and characterised as the hydroxyethylaniline ofthe formula ##STR26##

¹ H NMR (d₆ -DMSO): δ=2.77 (t, 2H); 3.18 (m, 2H); 3.42 (m, 2H); 3.60 (m,2H); 4.81 (t, OH); 4.83 (t, OH); 5.46 (t, NH); 6.50-6.63 (m, 2H); 7.15(m, 1H); 7.30 (m, 1H).

EXAMPLE 3

137 g of 2-(N-methylamino)thiophenol are dissolved in 200 ml of water byadding 120 ml of 40% sodium hydroxide solution. The resulting solutionis heated to 90° C. After the reaction space has been freed from oxygenby the passage of nitrogen, 50 g of ethylene oxide are introduced over aperiod of approx. 2-3 hours. The mixture is subsequently stirred for afurther 30 minutes at 90°-95° C. under a stream of N₂ and then cooled to40° C. The 2-hydroxyethyl 2-N-methylaminophenyl sulphide of thestructure ##STR27## which has separated out as an oil, is separated fromthe aqueous phase and can be used directly in this form as a couplingcomponent.

EXAMPLE 4

23.6 g of monosodium 7-amino-1,3-naphthalenedisulphonate are stirred in150 ml of water/50 g of ice and 20 ml of concentrated hydrochloric acid,and 17 ml of a sodium nitrite solution (300 g/l) are added dropwise at5° to 10° C. The diazotisation is complete after 1.5 hours. The smallexcess of nitrite is destroyed by adding amidosulphonic acid. Thecream-coloured suspension is adjusted to pH 2.5 with sodium carbonatesolution. A solution of 15.0 g of the free base of Example 2 in 100 mlof water, adjusted to pH 2.0, is added dropwise at approx. 10° C. Themixture is stirred for 4 to 5 hours at 10° C. (pH 1.5-2.0). To bring thecoupling reaction to completion, the pH is raised to 4.5 by addingsodium acetate and the mixture is stirred for a further 2 hours. 40 g ofsodium chloride are added, the mixture is stirred for 1 hour and theprecipitate is isolated by suction filtration. 48 g of a salt-containingdye of the formula ##STR28## are obtained after drying.

λmax=454 nm (H₂ O, pH 7-8)

¹ H NMR (d₆ -DMSO): δ=2.88 (t, 2H); 3.35 (t, 2H); 3.50 (t, 2H); 3.65 (m,2H); 5.15 (broad s, 20H); 6.17 (t, NH); 6.85 (d, 1H); 7.83-8.07 (m, 4H);8.16 (s, 1H); 8.30 (s, 1H); 9.30 (s, 1H).

EXAMPLE 5

7 g of the dye of Example 4 are stirred in 250 ml of water at pH 8-8.5,0.2 g of sodium tungstate is added and the mixture is heated to 70° C.30 ml of an approx. 35% aqueous hydrogen peroxide solution are addeddropwise. The temperature should be between 70° and 80° C. during thisprocess. After approx. 2 hours, the oxidation is checked by thin layerchromatography. The sulphoxide derivative formed as an intermediateduring the oxidation can also be detected. If appropriate, a further 10to 15 ml of hydrogen peroxide solution are added in order to oxidise theresidual sulphoxide derivative to the sulphone derivative. The mixtureis then stirred for 2 hours at 80° C., cooled to room temperature andacidified to pH 0.5 to 1.0 with dilute sulphuric acid. The dye is saltedout with 35 g of sodium chloride and 5 g of potassium chloride andisolated. 38 g of a salt-containing dye of the formula ##STR29## areobtained after drying. TLC and NMR show that the proportion of azoxy isonly a few percent.

νmax=406 nm (H₂ O, pH 7-8)

¹ H NMR (d₆ -DMSO): δ=3.42 (t, 2H); 3.55 (t, 2H); 3.68 (t, 2H); 3.75 (t,2H); 5.0-5.3 (broad, 2OH); 6.9 (broad s, NH); 7.13 (d, 1H); 7.98 (dd,1H); 8.05-8.17 (m, 2H); 8.20 (s, 1H); 8.27 (d, 1H); 8.32 (d, 1H); 9.35(d, 1H).

If the diazo component in Example 4 is now varied, other valuable dyesof azosulphide and azo/azoxysulphone structures can be preparedanalogously to the coupling instructions (Example 4) and oxidationinstructions (Example 5):

    __________________________________________________________________________     ##STR30##                                                                                                       ##STR31##                                  Ex.                                                                              D                   λmax (H.sub.2 O, pH 7-8)                                                          Ex.   λmax (H.sub.2 O, pH            __________________________________________________________________________                                            7-8)                                      ##STR32##          432 nm     11    396 nm                                7                                                                                 ##STR33##          406 nm     12    374 nm                                8                                                                                 ##STR34##          414 nm     13    397 nm                                9                                                                                 ##STR35##          448 nm     14    402, 455 (sh) nm                      10a                                                                               ##STR36##          446 nm      15a  404 nm                                10b                                                                               ##STR37##          448 nm      15b  404 nm                                __________________________________________________________________________

EXAMPLE 16

12.5 g of 4-aminobenzenesulphonic acid are diazotised analogously toExample 4 and the resulting suspension is adjusted to pH 2.5 with sodiumcarbonate solution. A solution of 15.0 g of the free base of Example 2in 100 ml of water, adjusted to pH 2.0, is added dropwise at 5° to 10°C. The mixture is stirred for 5 hours at pH 1.5 to 2.5 and at 10° C. andthen for 3 hours at pH 3.5 to 4.0 and at 10° C., the pH being raisedwith sodium acetate solution. When coupling is complete, the pH isadjusted to 8.0 with sodium carbonate solution. A clear solution of theazo dye of the formula ##STR38## is obtained.

0.2 g of sodium tungstate is added to the solution and the mixture isheated to 60° C. 35 ml of a 35% aqueous hydrogen peroxide solution aremetered in over a period of 15 minutes and the reaction is maintained at70° to 80° C. Oxidation to the sulphone is complete after approx. 3 to 4hours. The mixture is cooled to 20° C., adjusted to pH 6.0 and saltedout with 45 g of sodium chloride. After stirring for a further 2 hours,the precipitate is filtered off with suction and dried to give 32 g of agolden yellow dye powder of the structure ##STR39##

λmax=396 nm (H₂ O, pH 7-8)

¹ H NMR (d₆ -DMSO): δ=3.38 (t, 2H); 3.50 (t, 2H); 3.60-3.75 (m, 4H); 5.0(broad s, 20H); 6.94 (t, NH); 7.08 (d, 1H); 7.78 (m, 4H); 8.05 (dd, 1H);8.17 (d, 1H).

COMPOUNDS ACCORDING TO THE INVENTION EXAMPLE 17

35 g of the dye of Example 5 are added in portions to 50 ml of sulphuricacid monohydrate at 15°-25° C., with stirring, and the mixture isstirred for 2 hours at 20°-25° C. The red solution is then discharged onto 150 g of ice and 50 ml of water and the product is salted out with 20g of sodium chloride and isolated by suction filtration. The moist dyepaste is stirred in 150 ml of water and the mixture is neutralised withsolid sodium bicarbonate. After suction filtration and drying, 45 g of asalt-containing reddish brown reactive dye powder are obtained whichdyes cotton in golden yellow shades and to which the structure ##STR40##is assigned.

The dyes of Examples 11 to 15 can also be sulphated analogously toExample 17, giving yellow reactive dyes such as

EXAMPLE 18 ##STR41## EXAMPLE 19 ##STR42## EXAMPLE 20 ##STR43## EXAMPLE21 ##STR44##

This bifunctional reactive dye of Example 21 results from the sulphationof both the dye of Example 15a and that of Example 15b.

The same reactive dye 21 is also obtained if the dye of Example 10a or10b is added to sulphuric acid monohydrate, the requisite amount ofpotassium peroxodisulphate is added at 20° C., the mixture is stirredfor 2 hours at 40° C. and the product is worked up and isolated asdescribed (see Example 17).

A similarly important and valuable bifunctional reactive dye, which canbe prepared analogously, is

EXAMPLE 22 ##STR45## whose monofunctional intermediate of the structure##STR46## already dyes cotton in golden yellow shades of high fastness.

If the coupling component (Example 2) of the previous Examples isreplaced with 2-aminophenyl 2-hydroxyethyl sulphide (cf. European patent137 417) or with 2-N-methylaminophenyl 2-hydroxyethyl sulphide (Example3) and the azo dyes obtainable therefrom are oxidised and sulphatedanalogously to the instructions in Examples 5, 16 and 17, the followingvaluable yellow to golden yellow reactive dyes are obtained:

EXAMPLE 23 ##STR47## EXAMPLE 24 ##STR48## EXAMPLE 25 ##STR49## EXAMPLE26 ##STR50## EXAMPLE 27 ##STR51## EXAMPLE 28

4'-Amino-azobenzene-4-sulphonic acid is diazotised in known manner andcoupled with the component of Example 2 at pH 3-5. This solution of thedisazo dye of the structure ##STR52## is oxidised with hydrogen peroxidesolution in the presence of a catalytic amount of sodium tungstate, asdescribed in Example 5. The sulphone of the structure ##STR53## isisolated by salting-out and dried. Double sulphation analogously toExample 17 yields a disazo reactive dye which dyes cotton or wool inbrilliant orange shades with a high level of fastness and to which thefollowing structure is assigned: ##STR54## By varying the diazocomponent or using 2-aminophenyl 2-hydroxyethyl sulphide, other valuableorange or reddish brown disazo reactive dyes of the structure ##STR55##can be obtained (see Table). Fibre-reactive aminoazo compounds used asdiazo components are described e.g. in European patent document A-292

    __________________________________________________________________________    Ex.                                                                              D                 R.sup.1     R.sup.2   Y                                  __________________________________________________________________________    29                                                                                ##STR56##        H           H         CH.sub.2 CH.sub.2 OSO.sub.3 H      30                                                                                ##STR57##        H           H         CH.sub.2 CH.sub.2 OSO.sub.3 H      31                                                                                ##STR58##        H           SO.sub.3 H                                                                              "                                  32 "                 CH.sub.3    "         "                                  33                                                                                ##STR59##        CH.sub.3    H         CH.sub.2 CH.sub.2 OSO.sub.3 H      34 "                 H           H         H                                  35                                                                                ##STR60##        H           SO.sub.3 H                                                                              H                                  36 "                 CH.sub.3    H         CH.sub.2 CH.sub.2 OSO.sub.3 H      37 "                 OCH.sub.3   H         "                                  38 "                 OCH.sub.3   OCH.sub.3 "                                  39                                                                                ##STR61##        H           OCH.sub.3 "                                  40                                                                                ##STR62##        CH.sub.3    OCH.sub.3 CH.sub.2 CH.sub.2 OSO.sub.3 H      41                                                                                ##STR63##        Cl          H         "                                  42 "                 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3                                             H         "                                  43 "                 NHCOCH.sub.3                                                                              H         "                                  44 "                 NHCOCH.sub.3                                                                              OCH.sub.3 "                                  45 "                 NHCONH.sub.2                                                                              H         "                                  46                                                                                ##STR64##        CH.sub.3    H         CH.sub.2 CH.sub.2 OSO.sub.3 H      47                                                                                ##STR65##        H           H         H                                  48                                                                                ##STR66##        NHCOCH.sub.3                                                                              H         CH.sub.2 CH.sub.2 OSO.sub.3 H      49                                                                                ##STR67##        NHCOCH.sub.3                                                                              OCH.sub.3 CH.sub.2 CH.sub.2 OSO.sub.3 H      50                                                                                ##STR68##        CH.sub.3    SO.sub.3 H                                                                              "                                  51                                                                                ##STR69##        NHCOCH.sub.3                                                                              SO.sub.3 H                                                                              "                                  52                                                                                ##STR70##        H           SO.sub.3 H                                                                              "                                  53                                                                                ##STR71##        CH.sub.3    SO.sub.3 H                                                                              "                                  54                                                                                ##STR72##        CH.sub.3    SO.sub.3 H                                                                              "                                  55 "                 H           SO.sub.3 H                                                                              "                                  56                                                                                ##STR73##        H           SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3                                                    CH.sub.2 CH.sub.2 OSO.sub.3 H      57                                                                                ##STR74##        H           "         "                                  58                                                                                ##STR75##        H           "         "                                  59                                                                                ##STR76##        H           "         "                                  60 "                 NHCONH.sub.2                                                                              H         "                                  __________________________________________________________________________

Compound 56 can be prepared by diazotising the dye of Example 23 or itsnon-sulphated precursor, coupling the diazotised product with thecomponent of Example 2 and oxidising and sulphating the coupled product.

Alternatively, the thio precursor of the structure ##STR77## isdiazotised, the diazotised product is coupled with the compoundaccording to Example 2 and both hydroxyethylmercapto radicals of thedisazo dye are oxidised and sulphated. The above thio precursor is alsoobtained by coupling with 2-(N-sulphomethyl)aminophenyl 2-hydroxyethylsulphide and then saponifying the ω-methanoic acid group under alkalineconditions.

By varying the middle component, it is possible to obtain other valuabledisazo reactive components such as e.g.

EXAMPLE 61 ##STR78## EXAMPLE 62 ##STR79## EXAMPLE 63 ##STR80## EXAMPLE64 ##STR81## EXAMPLE 65 ##STR82## EXAMPLE 66

The dye base of the structure ##STR83## which can be prepared by thediazotisation of 5-acetylamino-2-aminobenzenesulphonic acid, couplingwith m-toluidine, diazotisation of the aminoazo compound, coupling withthe component of Example 2, oxidation with hydrogen peroxide,saponification of the N-acetyl group and sulphation of the hydroxyethylgroups, is stirred in water at pH 6.5 and reacted with a 1.2-fold molarexcess of 5-chloro-2,4,6-trifluoropyrimidine, the pH being kept constantat 6-7 by the addition of sodium carbonate solution. When the reactionis complete, the solid of the structure ##STR84## is salted out,isolated by suction filtration and dried.

It dyes cotton in reddish yellow shades. Other valuable bifunctionalreactive dyes, can be obtained by this process variant.

EXAMPLE 67 ##STR85## EXAMPLE 68 ##STR86## EXAMPLE 69 ##STR87## EXAMPLE70

2-Amino-5-aminomethyl-1-naphthalenesulphonic acid is diazotised inconventional manner and coupled with the coupling component of Example 2as in Example 3. After oxidation and sulphation of the monoazo compound,the product is condensed with an equimolar amount of5-chloro-4,6-difluoropyrimidine at pH 7-8. The hydrofluoric acidliberated is continuously neutralized by the addition of sodium,carbonate. The dye is salted out, filtered off with suction and dried.It dyes cotton in clear yellow shades and has the structure ##STR88##

Other important and useful bifunctional dyes which can be prepared inthe same way as described in Example 21 are as follows:

    ______________________________________                                         ##STR89##                                                                    Exam-                                                                         ple   R                Y                                                      ______________________________________                                        71    H                CH.sub.2 CH.sub.2 SO.sub.3 H                           72    H                CH.sub.2SO.sub.3 H                                     73    H                CH.sub.2CO.sub.2 H                                     74    H                CH.sub.2 CH.sub.2 CO.sub.2 H                           75    H                CH.sub.2 CH.sub.2 CH.sub.2 CO.sub.2 H                  76    CH.sub.2 CO.sub.2 H                                                                            CH.sub.2 CO.sub.2 H                                    77    H                CH(CO.sub.2 H)CH.sub.2 CO.sub.2 H                      78    H                                                                                               ##STR90##                                             79    H                                                                                               ##STR91##                                             80    H                CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2                                  OSO.sub.3 H                                            81    CH.sub.2 CO.sub.2 H                                                                            "                                                      82    CH.sub.2 CH.sub.2 SO.sub.3 H                                                                   "                                                      83    CH.sub.3         CH.sub.2 CH.sub.2 OSO.sub.3 H                          84    CH.sub.2 CO.sub.2 H                                                                            CH.sub.2 CH.sub.2 OSO.sub.3 H                          85    C.sub.2 H.sub.5  CH.sub.2 CH.sub.2 OSO.sub.3 H                          86                                                                                   ##STR92##       CH.sub.2 CH.sub.2 OSO.sub.3 H                          87    CH.sub.2 CH.sub.2 CO.sub.2 H                                                                   CH.sub.2 CH.sub.2 CO.sub.2 H                           88    CH.sub.2 CH.sub.2 CO.sub.2 H                                                                   CH.sub.2 CH.sub.2 OSO.sub.3 H                          ______________________________________                                    

Using the same method as described in Examples 17 and 28 the followingimportant and useful dyes can be prepared by variation of the radicals Rand Y in the coupling component.

EXAMPLE 89 ##STR93## EXAMPLE 90 ##STR94## EXAMPLE 91 ##STR95## EXAMPLE92 ##STR96## EXAMPLE 93 ##STR97## EXAMPLE 94 ##STR98## DYEING METHOD 1

2 parts of the dye obtainable according to Example 28 are dissolved in100 ml of water. The solution is added to 1900 parts of cold water, 60parts of sodium chloride are added and 100 parts of a woven cottonfabric are put into this dyebath.

The temperature is raised to 60° C., 40 parts of calcined sodiumcarbonate and a further 60 parts of sodium chloride being added after 30minutes. The temperature is kept at 60° C. for 30 minutes and the dyeingis then rinsed, soaped for 15 minutes in a boiling 0.3% solution of anion-free detergent, rinsed and dried to give a golden yellow dyeing withgood fastness properties.

DYEING METHOD 2

4 parts of the reactive dye prepared in Example 22 are dissolved in 50parts of water. 50 parts of a solution containing 5 g of sodiumhydroxide and 10 g of calcined sodium carbonate per liter are added. Awoven cotton fabric is padded with the resulting solution so that itsweight increases by 70%, and it is then wound on to a hatching roller.The cotton fabric is stored in this form for 3 to 12 hours at roomtemperature. The dyed goods are then rinsed, soaped at the boil for aquarter of an hour with a non-ionic detergent, rinsed again and dried togive a yellow dyeing with good fastness properties.

Deep black dyeings are obtained by using suitable mixtures of the dye ofExample 22 with C.I. Reactive Black 5.

EXAMPLE 95

a) A mixture composed of 10.0% of the dyestuff of the formula ##STR99##

(λ_(max) =440 nm (H₂ O))

13.5% of butylbenzyl phthalate and 76.5% of a condensation product ofadipic acid and 1,2-propanediol, which has a hydroxyl number of 112 to113 and an acid number of 0.31, is homogenised by stirring and thenground in a continuously operating commercial stirred ball mill, whichcontains glass beads 0.3 to 0.4 mm in diameter as grinding medium andthe shaft of which, provided with plane circular discs, is rotating at aspeed of 100 rpm, until the particle size of the dyestuff is less than 1to 2 μm.

In order to prepare a reddish-tinged yellow-coloured polyurethane foam,0.5% by weight of the dyestuff dispersion are fed via a separatemetering pump into the mixing chamber of the foaming apparatus accordingto German Patent Specification 901,471. After intensive mixing of thereactants (the formulations for a polyether foam and a polyester foamare described in the following paragraphs), a uniformly deepyellow-coloured foam of uniform pore width is obtained which isdistinguished by very good fastness to light and fastness to bleeding.

b) 100 g of a conventional trifunctional polyether, prepared fromtrimethylolpropane, propylene oxide and ethylene oxide (OH number 35), 4g of water, 0.6 g of a polysiloxane/polyalkylene block copolymer asstabiliser, 0.12 g of triethylenediamine as catalyst, 0.16 g of tinoctoate and toluylene diisocyanate in an amount which is stoichiometricwith respect to the amount of polyether and water used, are used toprepare a polyether foam.

c) The following components are used to prepare a polyester foam:

100 g of a polyester, prepared from adipic acid and diethylene glycol(OH number 50), 4 g of water, 1.4 g of N-methylmorpholine as catalyst,0.5 g of an emulsifier, which comprises an adduct of ethylene oxide witha mixture of higher alcohols and has an average molecular weight of 1100and an OH number of 52, 3.8 g of a sulphonated caster oil, 0.2 g ofparaffin oil and toluylene diisocyanate in an amount which isstoichiometric with respect to the amount of polyester and water used.

EXAMPLE 96

Dyestuff dispersions in which the adipic acid/propylene glycol adduct isreplaced by an adipic acid/propylene glycol adduct having a OH number of110 to 111 and an acid number of 0.2 or by a condensation product ofadipic acid and 1,3-butanediol having an OH number of 114 and an acidnumber of 0.36 are prepared as in Example 95.

Reddish-tinged yellow ether and ester foams which have outstandingfastness properties are obtained with these dyestuff dispersions also.

EXAMPLE 97

a) A yellow dyestuff paste composed of 20 g of the dyestuff mentioned inExample 95 and 80 g of a polyether, which is obtained by reaction of 1mol of trimethylolpropane and 3 mol of ethylene oxide and has an OHnumber of 550, is prepared as follows:

The dyestuff is kneaded in a dispersion kneader with an amount of theabovementioned polyether such that a viscous, kneadable mass is obtained(approximately 0.4 g of polyether per 1 g of dyestuff is used for thispurpose). After a kneading time of 10 minutes, the composition isdiluted very slowly with the remaining amount of polyether, withconstant kneading. A dyestuff paste is obtained which is used forcolouring rigid polyurethane integral foam.

b) 100 g of a polyol mixture which has OH number 495 and a viscosity of1150 mPa.s at 25° C., composed of 80 g of a polyether having OH number550, which has been obtained by an addition reaction of ethylene oxidewith trimethylolpropane, and 20 g of a polyester which has OH number 370and has been obtained by reaction of 1 mol of adipic acid, 2.6 mol ofphthalic anhydride, 1.3 mol of oleic acid and 6.9 mol oftrimethylolpropane, are mixed with 1 g of a polysiloxane/polyalkyleneoxide block copolymer as foam stabiliser, 0.5 g of tetramethylguanidineas catalyst, 5 g of monofluorotrichloromethane as propellant and 5 g ofthe dyestuff preparation described above. The mixture is fed to atwo-component metering mixing unit, in which, in order to prepare thefoaming reaction mixture, it is mixed intensively with 155 g of apolyisocyanate, which has been obtained by phosgenation ofaniline/formaldehyde condensation products and subsequent reaction witha diol having OH number 480, and has viscosity of 130 mPa.s at 25° C.and an NCO content of 28% by weight, and immediately introduced into ametal mould which is temperature-controlled at 60° C. After amould-release time of 7 minutes, the yellow-coloured moulding of rigidpolyurethane integral foam having a bulk density of 0.6 g/cm³ can bereleased from the mould. The mechanical properties (modulus ofelasticity, flexural strength, elongation at break, impact strength,heat distortion resistance and the like) of the coloured moulding arenot impaired compared with those of a moulded blank which has not beencoloured.

EXAMPLE 98

100 g of an ethanediol/butanediol/adipic acid polyester which has amolecular weight of 2000 (OH number 56) are stirred with a pastecomposed of 0.1 g of the dyestuff described in Example 95 and 22 g of1,4-butanediol and 1.2 g of n-octanol (0.037 mol, with respect to1,4-butanediol). 0.3 g of stearylamide and 1 g of stabiliser(2,6,2',6'-tetraisopropyldiphenylcarbodiimide) are also added and themixture is heated to 90° C. with stirring, and mixed with equivalentamounts of 4,4'-diphenylmethane diisocyanate (74.6 g with respect tototal OH) at 60° C. with vigorous stirring. The mixture is then castonto a metal sheet and the solidified product is granulated andinjection moulded.

A reddish-tinged yellow-coloured polyurethane elastomer moulding isobtained.

EXAMPLE 99

a) 482.5 g of hexanediol polycarbonate which has a molecular weight of1050 are dehydrated at 125° C. and 14 mmHg, 3.4 g of the dyestuffdescribed in Example 95are added at 120° C. and the mixture is stirredfor 10 minutes and allowed to cool to 100° C., 76.0 g of1,6-diisocyanatohexane are added and the mixture is held at 100° C. forone hour.

It is then cooled to 60° C., 4.0 g of N-methyldiethanolamine and 169.5 gof acetone are allowed to run in and the mixture is held at 60° C. for 3hours.

After further cooling to 50° C., 3.1 ml of dimethyl sulphate in 400 g ofacetone are added and the mixture is stirred for a further 20 minutes.

737 g of a 50% strength prepolymer solution in acetone which has an NCOcontent of 1.1% are obtained. 743 g of prepolymer are mixed with 165 gof 1N propylenediamine solution in water and 578 g of distilled water at45° C. while stirring well

The acetone is distilled off and the residue is washed with water,soaked through a 0.5 mm sieve, filtered off with suction and dried.

A reddish-tinged yellow, very free-flowing thermoplastic polyurethanepowder which has a melting point of 135° C. is obtained and is used fortextile coatings.

b) The powder described above (spherical particles having an averagediameter of 43 μm) is spread, using a doctor blade, on a release paper,the amount applied being 100 g/m², and then exposed to a temperature of140° C. in a duct 12 m long at a belt speed of 1.5 m/min. A porous filmforms which is viscoelastic, can be separated from the support withoutdifficulty and can be handled without any other means of support.

c) The film produced in accordance with paragraph b) is again coatedwith the same powder. (amount applied: 60 g/m²) in a second coatingoperation and is then treated at 170° C. in the duct as described in b).A homogeneous reddish-tinged yellow-coloured film which has a totalweight per unit area of 160 g/m² and has high tensile strength, verygood elastic properties and outstanding fastness to light is obtained.

d) The films formed in accordance with paragraphs b) and c) can bebonded in a conventional manner by wet-laminating on one or both sideswith any desired support materials, such as cotton weaves, polyesterweaves, fleece and the like. Polyurethane solutions, polyurethanedispersions or other adhesives are, for example, suitable forwet-laminating. However, lamination can also be carried out inaccordance with the principle of hot-sealing by means of thermoplasticpowders.

e) A porous film produced in accordance with paragraph b) is providedwith a coating of polyurethane powder from paragraph a) (amount applied80 g/m²) by doctor blade application and exposed to the effect of atemperature of 145° C. A cotton cheese cloth (80 g/m²) is laminated onunder pressure when the powder is in the plastic state. After cooling,the laminate is firmly bonded and withstands buckling more than1,000,000 in the Bally flexometer.

EXAMPLE 100

800 g of an adipic acid copolyester with 1,6-hexanediol and2,2-dimethyl-1,3-propanediol in a molar ratio of 65:35 (OH number=65.9),in which 0.8 g of the dyestuff described in Example 95 has been finelydispersed, are reacted for 1 hour at 60° C. and 3 hours at 70° to 80° C.with 15.5 g of N,N-bis-(β-hydroxy-propyl)-methylamine and 786 g of asolution of 260 g of diphenylmethane 4,4-diisocyanate in 650 g ofdimethylformamide, which had an NCO content of 9.21% after standing forone hour. The NCO content of the pre-adduct is then 2.37%, with respectto the solid substance.

37.7 g of terephthalic acid -bis-m-aminoanilide are stirred into 600 gof the above NCO pre-adduct solution at 50° C. and after 3 hours themixture is diluted with 20 g of dimethylformamide. After a further risein the viscosity, the mixture is diluted in each case withdimethylformamide until, after the addition of a total of 850 g ofdimethylformamide, a homogeneous elastomer solution having a viscosityof 64 Pa.s at 20° C. is obtained after about 20 hours. The inherentviscosity of the elastomer substance, measured inhexamethylphosphoramide in 1% strength solution at 25° C., is 1.30 dl/g.1% of acetic anhydride is added to the solution and the solution is spunby the conventional dry-spinning process, the fibres being wound,prestretched by 0 to 30% during the winding operation, onto spools andheatset in this state for one hour at 130° C. A further fraction of thesolution is spun by the wet-spinning process.

WET-SPINNING PROCESS

A 20% strength elastomer solution is spun at a throughput of about 1ml/min through a spinneret which has 20 holes 0.12 mm in diameter into ahot coagulating bath which is composed of 90% by weight of water and 10%by weight of dimethylformamide, is at 80° to 85° C. and is about 3 mlong, and wound at a take-off speed of 5 m/min after passing through awashing section (water/90° C.). The spools are kept in water at 50° C.for 1 hour and then dried.

DRY-SPINNING PROCESS

An elastomer solution, which is preferably 24 to 26% strength, is spunthrough a spinneret which has 16 holes 0.2 mm in diameter into a 5 mlong shaft which is heated to 220° to 250° C. and into which air atabout 210° to 280° C. is blown. The filaments are taken off at a speedof about 100 m/min and, following preparation with a talc suspension,with stretching if appropriate, are wound, for example at a speed of 125to 175 m/min. The filaments can then be subjected to a heatafter-treatment on spools or in continuous form. Higher spinning speeds,for example 300 to 400 m/min, can also be chosen, in which case it ispossible to dispense with a subsequent stretching process.

Reddish-tinged, yellow, highly elastic filaments are obtained which havevery good fastness to light and very good wet strength as well as verygood thermal, hydrothermal and mechanical properties.

EXAMPLE 101

35 g of the dyestuff described in Example 95 and 65 g of an 8.5%strength solution of a polyester polyurethane, which has been preparedby reaction of a polyester resin, obtained from hexanediol and adipicacid and having an average molecular weight of 800, with toluylene1,4-diisocyanate, in methylethyl glycol/toluene 1:1 are ground in a beadmill for 12 hours. The resulting dyestuff paste is suitable forpigmenting all commercially available two-component polyesterpolyurethane textile coating compositions.

b) 10 g of the yellow dyestuff paste described in paragraph a) arestirred slowly into a solution composed of 30 g of a crosslinkablepolyester polyurethane having terminal OH groups and 70 g of ethylacetate. After a short time (3 to 5 minutes), a stable dispersion isobtained which, after the addition of a polyisocyanate, prepared byreaction of 1 mol of trimethylolpropane with 3 mol of toluylenediisocyanate and a heavy metal salt as accelerator, is suitable forcoating textiles by the reversal or direct process. The polyurethanefilms produced by known processes using this dispersion are uniformlycoloured reddish-tinged yellow without specks and are fast to light andsolvents.

EXAMPLE 102

0.3% of the dyestuff described in Example 95 with respect to thepolyester content, are dissolved in a 35% strength solution of aphenol-capped polyisocyanate containing 12% NCO and a branched polyesterhaving a hydroxyl content of 12% in a weight ratio of 2:1 in equal partsof cresol, xylene and glycol monomethyl ether acetate. Thereddish-tinged yellow coloured paint is applied to aluminium foil withthe aid of a 10 μm coating roller system and then stoved for 30 minutesat 180° C.

The colour of the paint is retained even after stoving. The dyestuff isincorporated in the cured binder. On over-painting with a white stoveenamel, which is stored for 30 minutes at 130° C., no bleeding throughof the dyestuff is observed.

EXAMPLES 103 TO 126

In addition to the dyestuff used in the above examples, the dyestuffs inthe following table were also used successfully in accordance withExamples 95 to 102 for colouring polyurethane plastics in the indicatedhues.

    __________________________________________________________________________    Ex.                                                                              Diazo component                                                                             Coupling component       Hue   λ.sub.max              __________________________________________________________________________                                                    (DMF)                         103                                                                              4-(2-hydroxyethyl-                                                                          N,N-bis-(2-hydroxyethyl-)aniline                                                                       orange                                                                              462 nm                           sulfonyl-)aniline                                                          104                                                                              4-(2-hydroxyethyl-                                                                          N,N-bis-(2-hydroxyethyl)-3-methyl-aniline                                                              orange                                                                              471 nm                           sulfonyl-)aniline                                                          105                                                                              4-(2-hydroxyethyl-                                                                          N,N-bis-(2-hydroxypropyl-)aniline                                                                      orange                                                                              463 nm                           sulfonyl-)aniline                                                          106                                                                              4-(2-hydroxyethyl-                                                                          N,N-bis-(2-hydroxybutyl-)aniline                                                                       orange                                                                              463 nm                           sulfonyl-)aniline                                                          107                                                                              4-(2-hydroxyethyl-                                                                          N,N-bis-(2-hydroxyethyl)-3-acetyl-aminoaniline                                                         red orange                             sulfonyl-)aniline                                                          108                                                                              4-(2-hydroxyethyl-                                                                          N,N-bis-(2-hydroxyethyl)-2,5-dimethoxyaniline                                                          orange                                 sulfonyl-)aniline                                                          109                                                                              4-(2-hydroxyethyl-                                                                          N-(2-hydroxyethyl-)aniline                                                                             reddish                                sulfonyl-)aniline                      yellow                              110                                                                              4-(2-hydroxyethyl-                                                                          N-methyl-N-(2-hydroxyethyl-)-aniline                                                                   orange                                                                              459 nm                           sulfonyl-)aniline                                                          111                                                                              4-(2-hydroxyethyl-                                                                          N-ethyl-N-(2-hydroxyethyl-)aniline                                                                     orange                                                                              460 nm                           sulfonyl-)aniline                                                          112                                                                              4-(2-hydroxyethyl-                                                                          N-(2-cyanoethyl-)N-(2-hydroxy-ethyl-)aniline                                                           orange                                                                              456 nm                           sulfonyl-)aniline                                                          113                                                                              4-(2-hydroxyethyl-                                                                          2-(2-hydroxyethylthio-)N,N-bis-(2-hydroxyethyl-)ani-                                                   orange                                 sulfonyl-)aniline                                                                           line                                                         114                                                                              4-(2-hydroxyethyl-                                                                          N-benzyl-N-(2-hydroxyethyl-)-aniline                                                                   orange                                                                              458 nm                           sulfonyl-)aniline                                                          115                                                                              4-(2-hydroxyethyl-                                                                          N,N-bis-(2-(2-Hydroxyethyloxy)-ethyl-)aniline                                                          orange                                                                              464 nm                           sulfonyl-)aniline                                                          116                                                                              3-(2-hydroxyethyl-                                                                          N,N-bis-(2-hydroxyethyl-)-3-methylaniline                                                              reddish                                                                             451 nm                           sulfonyl-)aniline                      yellow                              117                                                                              3-(2-hydroxyethyl-                                                                          2-(2-hydroxyethylthio-)N-(2-hydroxyethyl-)aniline                                                      reddish                                                                             428 nm                           sulfonyl-)aniline                      yellow                              118                                                                              2-(2-hydroxyethylsulfonyl-)-                                                                N,N-bis-(2-hydroxyethyl-)3-methyl-aniline                                                              orange                                                                              467 nm                           aniline                                                                       2-(2-hydroxyethylsulfonyl-)-                                                                2-(2-hydroxyethylthio-)N-(2-hydroxyethyl-)aniline                                                      reddish                                                                             437 nm                           aniline                                yellow                              119                                                                              4-(2-hydroxyethylsulfonyl)-                                                                 2-(2-hydroxyethylthio-)N-(2-hydroxyethyl-)aniline                                                      reddish                                                                             436 nm                           3-methylaniline                        yellow                              120                                                                              4-(2-hydroxyethylsulfonyl)-                                                                 2-(2-hydroxyethylthio-)N-(2-hydroxyethyl-)aniline                                                      reddish                                                                             440 nm                           3-chloraniline                         yellow                              121                                                                              6-(2-hydroxyethylsulfonyl-)-                                                                2-(2-hydroxyethylthio-)N-(2-hydroxyethyl-)aniline                                                      reddish                                                                             402 nm                           naphthyl-2-amine                       yellow                                 6-(2-hydroxyethylsulfonyl-)-                                                                N,N-bis-(2-hydroxyethyl-)3-methylaniline                                                               orange                                                                              474 nm                           naphthyl-2-amine                                                           122                                                                              4-(2-hydroxyethylsulfonyl-                                                                  N,N-bis-(2-hydroxyethyl-)3-methylaniline                                                               yellow                                 methyl)-aniline                                                            123                                                                              4-[2-(2-hydroxyethyl-                                                                       N,N-bis-(2-hydroxyethyl-)3-methylaniline                                                               yellow                                 sulfonyl-)ethyl-]aniline                                                   124                                                                              4-(2-hydroxyethylsulfonyl-)-                                                                3-(2-hydroxyethylthio-)N-(2-hydroxyethyl-)aniline                                                      reddish                                aniline                                yellow                              __________________________________________________________________________

EXAMPLE 127 ##STR100##

A suspension of 140 g of the dyestuff from Example 95 is adjusted to pH3-4 in a solution of 2000 ml of water and 100 g of sodium chloride using4.1 g of sodium acetate and 3.0 ml of acetic acid and is then stirredwith 0.2 g of tungsten(VI) oxide and 140 ml of 35% strength hydrogenperoxide for 12 hours at room temperature. The resulting precipitate isfiltered off with suction and washed well with water. 120 g of thedyestuff of the above formula are obtained. λ_(max) (DMF): 420 nm.

The same result is obtained if 76 g of4-(2-hydroxyethylsulphonyl)-aniline are diazotised and coupled at 10° C.and pH 3-4 with 102 g of2-(2-hydroxyethylthio)-N-(2-hydroxyethyl)-aniline (80% strength product)and the dyestuff suspension thus obtained is oxidised with 140 ml ofhydrogen peroxide and 0.2 g of tungsten(VI) oxide for 12 hours at roomtemperature.

The resulting dyestuff is used for colouring analogously to Examples 95to 102, reddish-tinged yellow colourings being obtained.

EXAMPLE 128 ##STR101##

Analogously to the preparation in Example 127 the oxidation is carriedout for 1 hour at 85° C. Yield: 123 g, λ_(max) (DMF): 411 nm. Whencoloured in accordance with Examples 1 to 8, reddish-tinged yellowcolourings are obtained.

EXAMPLES 129 TO 138

If further thioethers are reacted analogously to Examples 127 to 128 togive sulphoxides or sulphones and these are used to colour polyurethaneplastics analogously to Example 95-102, dyestuffs of the formula

    D-N=N-K

are obtained which have the hues indicated in the following table.

    __________________________________________________________________________    Ex.                                                                              D             K                        Hue   λ.sub.max              __________________________________________________________________________                                                    (DMF)                         129                                                                              4-(2-hydroxyethylsulfonyl-)-                                                                2-(2-hydroxyethylsulfoxidyl)-N,N-bis-(2-hydroxy-)-                                                     reddish                                phenyle       aminophenyl-(4)          yellow                              130                                                                              4-(2-hydroxyethylsulfonyl-)-                                                                2-(2-hydroxyethylsulfonyl)-N,N-bis-(2-hydroxy-)-                                                       reddish                                phenyle       aminophenyl-(4)          yellow                              131                                                                              4-(2-hydroxyethylsulfonyl-)-                                                                3-(2-hydroxyethylsulfoxidyl)N-(2-hydroxyethyl-)-                                                       reddish                                phenyle       aminophenyl-(4)          yellow                              132                                                                              4-(2-hydroxyethylsulfonyl-)-                                                                3-(2-hydroxyethylsulfonyl-)N-(2-hydroxyethyl-)-                                                        reddish                                phenyle       aminophenyl-(4)          yellow                              134                                                                              3-(2-hydroxyethylsulfonyl-)-                                                                2-(2-hydroxyethylsulfoxidyl-)N-(2-hydroxyethyl-)-                                                      reddish                                                                             413 nm                           phenyle       aminophenyl-(4)          yellow                              135                                                                              3-(2-hydroxyethylsulfonyl-)-                                                                2-(2-hydroxyethylsulfonyl-)N-(2-hydroxyethyl-)-                                                        reddish                                                                             403 nm                           phenyle       aminophenyl-(4)          yellow                              136                                                                              2-(2-hydroxyethylsulfonyl-)-                                                                2-(2-hydroxyethylsulfonyl-)N-(2-hydroxyethyl-)-                                                        reddish                                                                             411 nm                           phenyle       aminophenyl-(4)          yellow                                 2-(2-hydroxyethylsulfonyl-)-                                                                2-(2-hydroxyethylsulfoxidyl-)N-(2-hydroxyethyl-)-                                                      reddish                                                                             421 nm                           phenyle       aminophenyl-(4)          yellow                              137                                                                              6-(2-hydroxyethylsulfonyl-)-                                                                2-(2-hydroxyethylsulfoxidyl-)N-(2-hydroxyethyl-)-                                                      reddish                                                                             422 nm                           naphthyl-2    aminophenyl-(4)          yellow                              138                                                                              6-(2-hydroxyethylsulfonyl-)-                                                                2-(2-hydroxyethylsulfonyl-)N-(2-hydroxyethyl-)-                                                        reddish                                                                             413 nm                           naphthyl-2    aminophenyl-(4)          yellow                              __________________________________________________________________________

We claim:
 1. A process for the preparation of a water-soluble reactivedye of structure (1):

    A--(SO.sub.2 X).sub.1 or 2                                 ( 1)

wherein A is a chromophoric azo, polyazo, anthraquinone or formazaneradical, and X is a CH=CH₂ or CH₂ CH₂ OSO₃ H,which comprises oxidizing amercapto compound of the formula

    A--(S--CH.sub.2 --CH.sub.2 --OH ).sub.1 or 2

to form a sulphonyl compound of the formula

    A--(SO.sub.2 --CH.sub.2 --CH.sub.2 --OH).sub.1 or 2,

sulphating said compound to produce a sulphate of the formula

    A--(SO.sub.2 --CH.sub.2 --CH.sub.2 --OSO.sub.3 H).sub.1 or 2,

or further reacting said compound with a base to produce avinylsulphonyl compound of the formula

    A--(SO.sub.2 --CH=CH.sub.2).sub.1 or
 2.


2. A process according to claim 1, whereinA is ##STR102## D is a benzeneor naphthalene diazo component, which can contain substituents otherthan OH, NH₂, monoalkylamino, dialkylamino and arylamino, and R is H, C₁-C₄ -alkyl, Cl--, OH--, CN--, CO₂ H--, OSO₃ H--, SO₃ H--, SO₂ X-- or C₁-C₄ -alkoxy-substituted C₁ -C₄ -alkyl, allyl, benzyl or OH--, CO₂ H-- orsulpho-substituted benzyl.